Chlorotrimethylsilane, Hexamethyldisilane, and 1,2-Dimethyl-1,1,2,2-tetraphenyldisilane as Oxidizing Agents in the Conversion of Hydrazines to 2-Tetrazenes. Trimethylsilyl Anion as a Leaving Group

Article abstract of DOI:10.1021/jo00266a014

The possibility of the Me3Si^- species to be a nucleofuge of a compound containing the NSiMe3 group was investigated.Treatment of hydrazines with 1.1 equiv of Me3SiCl, Me3SiSiMe3, or Ph2MeSiSiMePh2 in the presence of 1.0 equiv of potassium hydride gave the corresponding 2-tetrazenes (R¹R²NN=NNR¹R²) in fair to good yields.The hydrazines included 1-methyl-1-phenylhydrazine (9), 1-aminopiperidine (10), 1-amino-2,6-dimethylpiperidine (11), 4-aminomorpholine (12), and 1-aminohomopiperidine (13).In these reactions, Me3SiCl, Me3SiSiMe3, and Ph2MeSiSiMePh2 acted as oxidizing agents.Results from control experiments supported the proposed mechanism: silylation of hydrazines gave monosilylhydrazines, decomposition of monosilylhydrazines generated aminonitrenes, and dimerization of aminonitrenes afforded 2-tetrazenes.In the decomposition of monosilylhydrazines, Me3Si^- behaved as a leaving group from the NSiMe3 moiety.